Chain transfer agent for addition mass polymerization of polycycloolefinic monomers

a polycycloolefinic monomer and chain transfer agent technology, applied in the field of chain transfer agent for addition mass polymerization of polycycloolefinic monomers, can solve the problems of high molecular weight polymers, inability to use in many applications involving solvent-based compositions, and large amount of solid and liquid waste, so as to reduce the amount of initiators, and control the effect of polymerization activity

Active Publication Date: 2017-09-26
SUMITOMO BAKELITE CO LTD
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0012]Surprisingly, it has now been found that certain of the non-polar organic molecules and more specifically a series of substituted bicycloalkenes offer unique advantages as chain transfer agents to mass polymerize a variety of cyclic olefin monomers including but not limited to a variety of functionalized norbornene monomers. Among some of the advantages offered by these chain transfer agents (CTAs) include but are not limited to a) reducing the amount of the initiator to form the final polymer having very low levels of any residual metal initiator; b) controlling polymerization activity of the organo-metallic initiators employed; c) effective in reducing the molecular weight of the resulting polycycloolefinic polymers; d) readily tailorable to the required molecular weight of the polymer by controlling the reaction kinetics thereby resulting in minimum adverse effects on reaction kinetics and monomer conversion; e) low dielectric polymers can be formed; among others. In some aspects, the chain transfer agents as employed herein offers unique methods to form polymers exhibiting excellent fire retardant properties. In other aspects of this invention, the CTAs as employed herein provides hitherto unobtainable melt processable polycycloolefinic polymers. In further aspects of this invention, the CTAs of this invention provides for telechelic oligomeric and / or polymeric materials with end group functionalities having utility in various other applications.

Problems solved by technology

It is also known in the literature that certain of the aforementioned vinyl addition polymerization methods result in very high molecular weight polymers, which may not always be desirable, such as for example, high molecular weight polymers become less soluble in commonly used solvents, and therefore, can't be used in many applications involving any solvent based compositions.
These additional steps also create considerable amounts of solid and liquid waste which needs to be disposed, which are environmentally not friendly and also expensive.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Chain transfer agent for addition mass polymerization of polycycloolefinic monomers
  • Chain transfer agent for addition mass polymerization of polycycloolefinic monomers
  • Chain transfer agent for addition mass polymerization of polycycloolefinic monomers

Examples

Experimental program
Comparison scheme
Effect test

examples

[0250]The following abbreviations have been used hereinbefore and hereafter in describing some of the compounds, instruments and / or methods employed to illustrate certain of the embodiments of this invention:

[0251]DecNB: 5-decylbicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo-[2.2.1]hept-2-ene; PENB: 5-phenethylbicyclo[2.2.1]hept-2-ene; BCO—bicyclo[4.2.0]oct-7-ene; DANFABA—N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate; LiFABA—lithium tetrakis(pentafluoro-phenyl)borate; TBS—tri-n-butylsilane; THF—tetrahydrofuran; CTA—chain transfer agent; GPC: gel permeation chromatography; Mw—weight average molecular weight; PD—polydispersity; 1H NMR—proton nuclear magnetic resonance spectroscopy.

[0252]The following examples describe the procedures used for the preparation of various polymers as disclosed herein. However, it should be noted that these examples are intended to illustrate the disclosure without limiting the scope thereof.

[0253]The following Examples 1 to 11 illustrate the mas...

examples 1-5

[0254]The following Examples 1-5 demonstrate the effects of various levels of BCO on homopolymer molecular weight.

[0255]Into a suitable reactor purged with nitrogen were placed 5000 parts of DecNB, one part of palladium compound (AcO—Pd—NCCH3(P-i-Pr3)2B(C6F5)4) and 2 parts of DANFABA. To this mixture was then added desirable amounts of BCO ranging from 1 mole percent to 7.5 mole percent based on the amount of monomer employed, as summarized in Table 1. The reaction mixture was then heated to 85° C. and maintained at this temperature for 30 minutes and then heated to 110° C. and maintained at that temperature for 30 minutes. After which time the reaction mixture was allowed to cool to room temperature. The resulting products in each of the Examples 1 to 5 were characterized by GPC in THF, the Mw and PD for each of the Examples 1 to 5 are summarized in Table 1. The thermal stability of each of the polymer products from Examples 1 to 5 were also analyzed by TGA, the temperature at whic...

examples 6-11

[0260]The procedures of Examples 1 to 5 were substantially repeated in these Examples 6 to 11 except that (iso-propoxy-dicyclopentadienyl)chloropalladium(triisopropyl)phosphine [Pd(i-PrO-DCPD)Cl(P-i-Pr3)] was used as the palladium initiator in combination with LiFABA in the ratio of 5000 parts of DecNB as the monomer, 1 part of palladium compound and 1 part of LiFABA. In addition, the mole percent of BCO employed were varied as summarized in Table 2. Also summarized Table 2 are the percent weight loss of the monomer, the Mw and PD as determined by GPC of each of the polymer products obtained and the 5% weight loss of the polymer product as determined by the TGA.

[0261]

TABLE 2Example Mol % % Weight GPCTGA, °C.No.BCOLossMw / PD(5% weight loss) 614.554,000 / 3.5369 73.34.836,000 / 3.5368 84529,000 / 3.4365 955.122,000 / 3354107.56.915,000 / 2.734611106.613,000 / 2.8345Comp. Ex. 207Insoluble363

[0262]It is again evident that BCO acts as an effective chain transfer agent in Examples 6-11. Furthermore, t...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

PropertyMeasurementUnit
mol %aaaaaaaaaa
molar ratioaaaaaaaaaa
boiling pointaaaaaaaaaa
Login to view more

Abstract

The present invention relates to use of certain chain transfer agents to control molecular weight of addition mass polymerization of certain polycycloolefinic monomers. More specifically, the present invention relates to use of a series of substituted bicycloalkenes as chain transfer agents in the addition mass polymerization of a series of functionalized norbornene-type monomers. This invention also relates to compositions containing bicycloalkenes as chain transfer agents in forming “in mold” polycycloolefinic polymers by addition mass polymerization.

Description

CROSS REFERENCE TO RELATED APPLICATIONS[0001]This application claims the benefit of U.S. Provisional Application No. 62 / 140,514, filed Mar. 31, 2015, which is incorporated herein by reference in its entirety.BACKGROUND OF THE INVENTION[0002]Field of the Invention[0003]The present invention relates to use of certain chain transfer agents to control molecular weight of addition mass polymerization of certain polycycloolefinic monomers. More specifically, the present invention relates to use of a series of substituted bicycloalkenes as chain transfer agents in the addition mass polymerization of a series of functionalized norbornene-type monomers. This invention also relates to compositions containing bicycloalkenes as chain transfer agents in forming “in mold” polycycloolefinic polymers by addition mass polymerization.[0004]Description of the Art[0005]Cyclic olefin polymers, such as polynorbornenes (PNBs), are widely used in a variety of electronic, optoelectronic and other applicatio...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Patents(United States)
IPC IPC(8): C08F132/08C08F2/02C08F2/38
CPCC08F132/08C08F2/02C08F2/38C08F4/12C08F4/60027C08F4/60031C08F4/7095
Inventor NG, HENDRASETO, KEITAROZHANG, WEI
Owner SUMITOMO BAKELITE CO LTD
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap